Journal of the European Ceramic Society 24 (2004) 271276 www.elsevier.

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(Ba,Sr)TiO3 thin lm growth in a batch processing MOCVD reactor

S. Regnerya,b,*, P. Ehrharta, F. Fitsilisa, R. Wasera, Y. Dingc, C.L. Jiac, M. Schumacherb, F. Schienleb, H. Juergensenb
a

IFF/EKM-Forschungszentrum Ju lich, Germany b Aixtron AG Aachen, Germany c IFF/MSF-Forschungszentrum Ju lich, Germany

Abstract Thin lms of dierent compositions within the (Bax,Sr1x)TiO3 solid solution series were deposited in a planetary multi-wafer MOCVD reactor using dierent solutions of Sr(thd)2, Ba(thd)2 and Ti(O-i-Pr)2(thd)2 precursors. Structural and electrical properties of Pt/BST/Pt MIM structures are presented. On the base of lm thickness series ranging from 10 to 150 nm the electrical permittivity is discussed within the dead layer model. The performance of two dierent liquid precursor delivery systems, characterized by ash evaporation and liquid injection, respectively, are compared for the example of dierent SrTiO3 lms. Finally, the growth of SrTiO3 on Pt(111) is compared with the growth on Si(100) and the electrical characteristics of the Pt/STO/Si MIS structures are discussed. # 2003 Elsevier Ltd. All rights reserved.
Keywords: BaTiO3 and titanates; Capacitors; Dielectric properties; Electron microscopy; Thin lms

1. Introduction High dielectric constant perovskite thin lms, such as the BaxSr1xTiO3, (BST), solid solution series have been proposed for a very broad application area, including capacitor dielectrics for future dynamic random access memories (DRAMs), embedded capacitors, tunable devices, as well as gate oxides for eld eect transistors (FETs).1 For capacitor applications, i.e. metal-insulatormetal (MIM) structures, there is a wide experience on the growth on suitable electrodes, and Pt might be considered as a standard metal. For gate-oxide applications metal-insulator-semiconductor (MIS) structures must be deposited. An ultra thin oxide layer should be grown directly on Si without interfacial SiOx layers, which reduce the capacitance of the layer stack.2 Amorphous metal oxides, like Al2O3, HfO2, and ZrO2, with K-values in the range of 820, are considered as the most promising near term replacement of the presently used SiO2. For even higher K-values crystalline materials, especially SrTiO3 (STO), are considered as epitaxial layers and, in spite of the possible complications by grain boundaries, also in the form of polycrystalline lms. In order to optimize the growth conditions for the dierent applications of these lms we investigated the
* Corresponding author. E-mail address: s.regnery@fz-juelich.de (S. Regnery). 0955-2219/03/$ - see front matter # 2003 Elsevier Ltd. All rights reserved. doi:10.1016/S0955-2219(03)00235-8

metal organic chemical vapor deposition (MOCVD) of thin BST lms of dierent composition and on dierent substrates. We rst report on the growth of (Ba,Sr)TiO3 on Pt(111) and the electrical properties of the resulting MIM structures. Secondly we compare STO lms deposited with dierent evaporation systems and nally we compare the growth of STO on Pt(111) and Si(100) substrates.

2. Experimental 2.1. Film deposition Films were deposited in a Aixtron 2600G3 Planetary Reactor1, which can handle ve 6-inch wafer simultaneously. This reactor is characterized by a central gas inlet providing a pure horizontal gas ow, which makes this reactor a radial ow system.3 The process conditions are summarized in Table 1. The deposition temperature is characterized by the suszeptor temperature, however, the actual wafer surface temperature may deviate by several degrees and depends on the details of the process and on the wafer surface, for example, platinized wafers have somewhat higher temperatures than oxidized wafers. The lm composition was routinely determined by XRF and lm thickness growth rates and precursor incorporation eciencies were deduced from these data.

272 Table 1 Growth conditions

Susceptor temperature Reactor pressure Film thickness

S. Regnery et al. / Journal of the European Ceramic Society 24 (2004) 271276

650  C 12 mbar 10150 nm ATMI-300B TRIJET1 240  C 11.3 1.9 ml/min (typically 0.05 molar)

Vaporization temperature Growth rate [nm/min] Liquid source feeding rate

240  C 2.7 0.08 ml/min (typically 0.35 molar)

Two vaporizer systems were compared. In the rst case we used a liquid delivery system, ATMI-300B which mixes the liquid precursors of up to four dierent sources, in our case 0.35 molar solutions of Sr(thd)2, Ba(thd)2 and a 0.4 molar solution of Ti(O-iPr)2(thd)2. The liquid mixture is delivered by a micro-pump to the vaporizer, which is basically a sintered metal frit heated at 240  C. Once in contact with the frit the precursor evaporates abruptly. In order to avoid clogging of the frit the evaporation rate is limited to about 0.08 ml/s which limits also the growth rate for our 56 inch reactor. In the second case we use a TRIJET1 vaporizer. Due to the non-contact evaporation clogging is prevented and rather high evaporation rates can be achieved. Four independent inject valves directly feed into the vaporization chamber. For deposition of STO we used the same precursors as in the previous case, but for reliable processing a higher dilution is recommended and a 0.05 molar solution was used. The amount of precursor delivery depends on the source pressure (1100 mbar), the opening time of the inject valves (0.8 ms) and the frequency of injection pulses. After optimizing the deposition process and especially the homogeneity on the 6 inch wafers we used 6.25 pulses per second, which is 3.125 pulses per second of each of the two sources used for STO. The main advantage for our applications are the separate injection valves which allow for a variability concerning source selection and concentration during lm growth. 2.2. Electrical properties For the electrical characterization Pt top electrodes were deposited by magnetron sputtering. Electrode size of a diameter between 0.1 and 1.13 mm were obtained by lift-o process. For the Pt/BST/Pt MIM structures an additional post-annealing process was performed, generally at 550  C for 20 min in oxygen. For the Pt/BST/Si MIS structures grown on p-type Si(100) an eutectic GaIn alloy was used to form an ohmic contact to the Si backside electrode. The CV characteristics were measured with a HP4284A LCR meter. For the MIM structures a standard frequency of 1 kHz was

used whereas 100kHz were applied for the MIS structures in order to reach the HF characteristics. It is generally observed that the permittivity of high-K thin lms capacitors shows some thickness dependence, which can be phenomenological described by an interfacial layer. This model assumes a bulk region of thickness, t, and the two interface regions adjacent to the electrodes with thickness, ti, which yield two capacitors of a lower permittivity. Considering the two electrodes as identical the resulting reciprocal capacitance of the lm is given by Eq. (1). By further approximating (t2ti) by t, the slope of a plot of 1/C versus thickness reveals the bulk permittivity, while the intercept represents the interface capacitance, 2A=Ci or the value of 2ti ="0 "i . A 2A A 2 ti t 2t C Ci CB "0 "i "0 "B 1

In the following we will consider the values of "i/ti, which represent an average of the two interfaces.

3. Experimental results 3.1. BST on Pt(111) The growth behavior of (Ba0.7Sr0.3)TiO3, short BST(70/30), had been investigated in detail previously4 and we concentrate here on depositions at a temperature of 655  C. These lms were generally characterized by a nearly perfect (100)-texture and Fig. 1 summarizes the changes of the XRD diagrams with changing (Ba/ Sr) ratio. All lms were grown at 655  C with a thickness between 23 and 26 nm. The composition was slightly GrII rich (GrII/Ti=1.011.05) and the (Ba/Sr) ratio was varied from 70/30 to 0/100 (pure STO) as indicated in the gure. With decreasing Ba content we observe the expected shift of the (h00) peaks, and the decrease of the height of the (100) superstructure reection as compared to the (200) fundamental reection. For low Ba content there is in addition some indication of the (110) reection; these deviations from the perfect (100)-texture indicate a less stable growth. TEM micrographs, Fig. 2, show in addition, that for pure STO these dierent lm orientations are formed both in the nucleation phase (Fig. 2a), as well as during further lm growth (Fig. 2b). Due to this disruption of the columnar growth there is a trend for a more random texture for thicker lms. However, there is no transition to a (111)-texture which might be expected due to the perfect lattice match in this stoichiometry region and which has been observed for CSD grown SrTiO3 lms.5 The eective permittivity of these lms decreases from values of 200240 for BST(70/30) to values of 120150 for pure STO. No signicant dependency on variations of the texture of the STO lms was revealed.

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Fig. 1. XRD-diagrams of BST lms with thickness of %30 nm deposited at 655  C. Films are shown with decreasing Ba content as indicated in the gure.

Fig. 2. Cross-sectional HRTEM images of the STO/Pt lms: (a) nucleation of dierent grain orientations at the Pt/STO interface. (b) Occasional disruption of the columnar growth in STO lms.

3.2. STO deposition on Pt(111) with dierent vaporizers In order to allow a detailed discussion of the electrical lm properties thickness series are necessary in order to separate eects of the interface and the bulk. Therefore several STO thickness series were performed. Fig. 3a compares the reciprocal capacity of two series for slightly Gr-II rich lms as obtained for optimized conditions with the dierent vaporizers (Table 1). Fig. 3b shows the results for Ti-rich lms as compared to the Gr-II rich lms both obtained with the TRIJET1. Again no signicant dierence could be observed. The quantitative results are summarized in Table 2 and are discussed later. Additional thickness series were performed with the TRIJET1 vaporizer in order to test changes of the

Table 2 Results of dierent thickness series Substrate Pt(111) Film BST 70/30 Vaporizer ATMI-300B ATMI-300B ATMI-300B TRIJET1 TRIJET1 ATMI-300B GrII/Ti range 1.031.10 0.910.95 1.011.05 1.011.05 0.920.99 0.881.12 " (bulk) 45020 83710 20810 21510 20810 200100 "i/ti (nm1) 286 144 416 265 346 0.9a

STO

Si(100)

STO

a For this value it is assumed that the main inuence of the interface results from the transition between silicon and STO, hence the inuence to the platinum interface was neglected.

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3.3. STO on Si(100) Independent of the pretreatment, i.e. a native oxide layer or a HF-dip before deposition, an oxide layer of 23 nm thickness is observed between the p-type Si and the STO, Fig. 4 (for details see Ref. 6). The grain size of these STO lms is smaller and more randomly distributed than for depositions on Pt. XRD peaks are much better resolved in a thin lm geometry and Fig. 5 shows as an example a 20 nm thick STO lm measured with an incident angle of 2 . The dierences in peak width and texture become obvious from a comparison to the sharp peaks in Fig. 1. The planetary reactor in principle allows the deposition on both substrates simultaneously. In case of the ATMI vaporizer the strontium eciency was slightly increased compared with depositions on platinum (7%) whereas the Ti eciency was slightly decreased (1%). Hence, the resulting lms were slightly more Sr-rich than the lms deposited on Pt. For the Trijet1 vaporizer major dierences were observed: the strontium eciency showed the same tendency (2.5%) but the Ti eciency was about 31% reduced on Silicon substrates. This dierent behavior of the two vaporizers is not yet understood and might be due to the increased solvent concentration or the higher growth rate in combination with possible catalytic eects in the case of the Pt interface. A typical CV curve for the Pt/STO/SiOx/p-Si/(GaIn) MIS structure is shown in Fig. 6. For the following discussion we extracted the capacitance in the accumulation region for a comparison to the MIM structures, Table 2. Fig. 7 summarizes the capacity data for several lms in a 1/C plot. As compared to Fig. 3 we observe a small interfacial capacity, which in this case corresponds to the SiOx layer (Fig. 4) and, in spite of the large uncertainty due to the limited thickness range, the slope yields a similar bulk value for the STO lm as for the MIM structures.

Fig. 3. Reciprocal capacitance for dierent STO thickness series. (a) Sr-rich lms deposited with the ATMI-300B and the TRIJET1 respectively. (b) Comparison of Ti-rich lms to Sr-rich lms (data of part a) both deposited with the TRIJET1 vaporizer.

growth sequence: (a) the sequence was changed from a simultaneous deposition to alternating growth of each element: the deposition time for a monolayer was estimated from the average growth rates and monolayers of strontiumoxide or titaniumoxide were deposited with an interrupt of 5 s between the activation of the dierent sources. (b) Deposition of a Sr-rich interfacial layer: an interface layer (Sr/Ti=1.2) of a thickness of 2 nm at the electrodes, and a bulk stoichiometry of Sr/Ti=0.98. This prole was qualitatively established by STEM with a Philips CM20-FEG electron microscope. However, both variations did not result in a signicant change of the electrical properties of the STO lms.

Fig. 4. HRTEM image of the STO/SiOx/Si interface.

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Fig. 5. XRD of a 20 nm STO/SiOx/Si lm in glancing entrance (2 ) geometry.

Fig. 6. CV curve of a typical Pt/STO/SiOx/p-Si/(GaIn) lm stack with 20 nm STO thickness.

Fig. 7. Reciprocal capacitance for a STO/Si thickness series.

4. Discussion and conclusion The electrical properties as determined from lm thickness series are summarized in Table 2 in terms of the bulk permittivity, ", and the interfacial capacity, which is expressed by "i =ti . For BST(70/30) we observe a clear indication of a stoichiometry dependence, a decrease of the interfacial capacitance and an increase of the bulk permittivity with increasing Ti content of the lms.4 This tendency cannot be observed for the present STO lms, and this observation is independent of the deposition method. This dierence indicates that the incorporation of the Ba atoms must be responsible for the changes in the interfacial properties. However, it must be kept in mind, that the values of "i =ti for the STO lms are always at the upper limit of the values obtained for BST(70/30). In addition we observe no signicant changes with a change of the interface

stoichiometry or the growth mode which are possible with the TRIJET1 vaporizer. However, this missing eect of the interface stoichiometry is consistent with the independence from the average stoichiometry for the STO layers (Fig. 3b). As these results for the MIM structures were obtained only after annealing of the lms after top electrode deposition, dierent annealing procedures after top electrode deposition have been tested: 650  C anneals in oxygen or articial air did not yield higher values. Some tests were accomplished on electrodes with evaporated platinum electrodes. The bulk permittivity was within the error the same but the interface capacity was much reduced. This dierence may be related to the surface cleaning property of sputtering. The physical origin of the dead layer is still under debate and quite dierent models have been proposed (see e.g. Ref. 7). The observed values of "i =ti =30 nm1 correspond to a permittivity of 3 for a subatomic layer thickness of 0.1 nm, which cannot be detected by analytical methods. On the other hand assuming a signicant thickness of the interfacial layer of 1 nm the permittivity would already reach a high-K value of 30. Hence, the physical thickness of the low-K region must be very thin. In the last line of Table 2 we show the results of the thickness series on silicon. Within the errors there is no dierence between untreated Si(100) and on HF dipped silicon. As only lms with thickness in the limited range of 1227 nm are available the bulk permittivity has a large uncertainty, but it is still within the same range in spite of the much smaller grain size. In contrast to the platinumSTO interface the siliconSTO interface is characterized by an SiOx layer which is clearly visible in the TEM. This amorphous interlayer had a typical thickness of 23nm (Fig. 4). If we accept this value we obtain "r=2.7 for the interfacial layer which somewhat lower than the value of 3.9 expected for perfect SiO2. Vice versa if we assume a "r of 3.9 for SiO2 we get an interface thickness of 4.3 nm. Although this interfacial layer corroborates the total capacity of the stack it is shown that rather high-K STO can be grown on silicon.

Acknowledgements It is a pleasure to appreciate the help of W. Krumpen in the XRF analysis of the lms. References
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S. Regnery et al. / Journal of the European Ceramic Society 24 (2004) 271276 5. Jia, C. L., Urban, K., Homann, S. and Waser, R., Microstructure of columnar-grained SrTiO3 and BaTiO3 thin lms prepared by chemical solution deposition. J. Mater. Res., 1998, 13, 22062217. 6. He, J. Q., Regnery, S., Jia, C. L., Qin, Y. L., Fitsilis, F., Ehrhart, P., Waser, R., Urban, K. and Wang, R. H., Interfacial and microstructural properties of SrTiO3 thin lms grown by MOCVD on Si(100) substrates. J. Applied Physics, 2002, 92, 72007205. 7. Shinamon, L. J., Bowman, R. M. and Gregg, J. M., Investigation of dead-layer thickness in SrRuO3/Ba0.5Sr0.5TiO3/Au thin lm capacitors. Appl. Phys. Lett., 2001, 78, 17241726.

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